Poly(arylene ether) method

Abstract

A method of preparing a capped poly(arylene ether) is described. By controlling the order of addition and rates of addition of reactants, solvent, and catalyst, problems associated with known methods are avoided. The method is particularly suitable for large-scale preparations of a capped poly(arylene ether).

1 . A method of preparing a capped poly(arylene ether), comprising:
 adjusting the temperature of a solvent to a temperature in the range of about 30° C. to an atmospheric boiling point of the solvent;   combining a poly(arylene ether) with the temperature-adjusted solvent and agitating to at least partially dissolve the poly(arylene ether);   combining a capping catalyst with the combined poly(arylene ether) and solvent;   combining a capping agent with the combined poly(arylene ether), solvent, and capping catalyst; and   maintaining the combined capping agent, poly(arylene ether), solvent, and capping catalyst at about 60 to about 150° C. for about 40 to about 120 minutes to form a solution of the capped poly(arylene ether).   
     
     
         2 . The method of  claim 1 , wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises adding the poly(arylene ether) to the solvent at a rate of about 0.4 to about 2 weight percent of the total poly(arylene ether) per minute. 
     
     
         3 . The method of  claim 1 , wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises combining a poly(arylene ether) solution with the temperature-adjusted solvent. 
     
     
         4 . The method of  claim 1 , wherein said combining a poly(arylene ether) with the temperature-adjusted solvent is conducted in an atmosphere comprising less than or equal to 10 kilopascals partial pressure of molecular oxygen. 
     
     
         5 . The method of  claim 1 , wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises adding the poly(arylene ether) to the solvent via an apparatus comprising a dispensing valve with an open/close controller, and a nitrogen-purged conduit. 
     
     
         6 . The method of  claim 5 , wherein the apparatus further comprises a hopper and a rotary valve. 
     
     
         7 . The method of  claim 1 , wherein said agitating to at least partially dissolve the poly(arylene ether) comprises agitating the combined poly(arylene ether) and solvent at about 50 to about 100° C. for about 10 to about 100 minutes. 
     
     
         8 . The method of  claim 1 , wherein said agitating to at least partially dissolve the poly(arylene ether) comprises mixing with a mixing energy of about 10 to about 50 kilojoules per kilogram total of poly(arylene ether) and solvent. 
     
     
         9 . The method of  claim 8 , further comprising heating the combined poly(arylene ether) and solvent with a heating energy of about 100 to about 250 kilojoules per kilogram total of poly(arylene ether) and solvent. 
     
     
         10 . The method of  claim 1 , wherein said at least partially dissolving the poly(arylene ether) comprises dissolving at least about 80 weight percent of the poly(arylene ether). 
     
     
         11 . The method of  claim 1 , wherein said combining a capping agent comprises adding the capping agent to the poly(arylene ether), solvent, and capping catalyst at a rate effective to maintain a temperature no more than 10° C. greater than a temperature in the absence of capping agent addition. 
     
     
         12 . The method of  claim 1 , wherein said combining a capping agent comprises adding the capping agent in an amount comprising an excess to compensate for a water impurity in at least one of the solvent, the poly(arylene ether), and the capping catalyst. 
     
     
         13 . The method of  claim 1 , wherein said combining a capping agent comprises using at least 0.8 mole of capping agent per 1 mole total for the sum of moles of phenolic end-groups in the poly(arylene ether), moles of water in the poly(aryiene ether), and moles of water in the solvent. 
     
     
         14 . The method of  claim 1 , wherein the solvent is selected from the group consisting of halogenated aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated aromatic hydrocarbon solvents, and mixtures thereof. 
     
     
         15 . The method of  claim 1 , wherein the solvent is toluene. 
     
     
         16 . The method of  claim 1 , wherein the solvent is styrene. 
     
     
         17 . The method of  claim 1 , wherein the capped poly(arylene ether) comprises repeating structural units having the formula 
       
         
           
           
               
               
           
         
       
       wherein for each structural unit, each Z 1  is independently halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and each Z 2  is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms. 
     
     
         18 . The method of  claim 1 , wherein the capped poly(arylene ether) comprises 2,6-dimethyl-1,4-phenylene ether units, 2,3,6-trimethyl-1,4-phenylene ether units, or a combination thereof. 
     
     
         19 . The method of  claim 1 , wherein the capped poly(arylene ether) has the structure 
       
         
           
           
               
               
           
         
       
       wherein x is 5 to about 100; each occurrence of Q 1  is independently halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q 2  and R 6  and R 7  is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and R 1  has the structure 
       
         
           
           
               
               
           
         
       
       wherein n is 0 or 1, R 2  is C 1 -C 12  hydrocarbylene, and R 2  and R 3  and R 4  are each independently hydrogen or C 1 -C 18  hydrocarbyl. 
     
     
         20 . The method of  claim 1 , wherein the capped poly(arylene ether) has the structure 
       
         
           
           
               
               
           
         
       
       wherein x is 5 to about 100. 
     
     
         21 . The method of  claim 1 , wherein the capped poly(arylene ether) has the structure 
       
         
           
           
               
               
           
         
       
       wherein z is 0 or 1; each occurrence of x is independently 1 to about 100; each occurrence of Q 1  is independently halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of Q 2  and R 6  and R 7  is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl with the proviso that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; each occurrence of R 1  is independently 
       
         
           
           
               
               
           
         
       
       wherein n is 0 or 1, R 2  is C 1 -C 12  hydrocarbylene, and R 2  and R 3  and R 4  are each independently hydrogen or C 1 -C 18  hydrocarbyl; and Y has a structure selected from 
       
         
           
           
               
               
           
         
       
       wherein each occurrence of R 8 , R 9 , and R 10  is independently selected from hydrogen and C 1 -C 12  hydrocarbyl. 
     
     
         22 . The method of  claim 1 , wherein the capped poly(arylene ether) has the structure 
       
         
           
           
               
               
           
         
       
       wherein each occurrence of x is independently 1 to about 50. 
     
     
         23 . The method of  claim 1 , wherein the poly(arylene ether) has an intrinsic viscosity of about 0.05 to about 1.0 deciliter per gram, measured at 25° C. in chloroform. 
     
     
         24 . The method of  claim 1 , wherein the poly(arylene ether) comprises a first poly(arylene ether) having an intrinsic viscosity of about 0.05 to less than 0.2 deciliter per gram and a second poly(arylene ether) having an intrinsic viscosity of 0.2 to about 0.6 deciliter per gram, wherein the intrinsic viscosities are measured at 25° C. in chloroform. 
     
     
         25 . The method of  claim 1 , wherein the capping catalyst is selected from dialkylaminopyridines, pyrollidinopyridines, and mixtures thereof. 
     
     
         26 . The method of  claim 1 , wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises providing the poly(arylene ether) as powder and pellets. 
     
     
         27 . The method of  claim 1 , wherein the capping agent has the structure 
       
         
           
           
               
               
           
         
       
       wherein each occurrence of R 11  is C 1 -C 12  hydrocarbylene; each occurrence of R 12  is independently hydrogen or methyl; each occurrence of R 13  and R 14  are independently hydrogen or C 1 -C 12  hydrocarbyl; m is 0 or 1; and X is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
       wherein R 11 , R 12 , R 13 , R 14 , and m are defined as above. 
     
     
         28 . The method of  claim 1 , wherein the capping agent is methacrylic anhydride. 
     
     
         29 . The method of  claim 1 , wherein said combining a capping agent comprises combining the capping agent with the poly(arylene ether), solvent, and capping catalyst over the course of about 10 to about 45 minutes. 
     
     
         30 . The method of  claim 1 , wherein the solvent and the poly(arylene ether) are used in a weight ratio of about 1:3 to about 9:1, wherein the capping agent and the capping catalyst are used in a molar ratio of about 4:1 to about 10:1, and wherein the poly(arylene ether) and the capping agent are used in amounts such that a molar ratio of capping agent to hydroxy groups in the poly(arylene ether) is about 1.5:1 to about 5:1. 
     
     
         31 . The method of  claim 1 , further comprising monitoring consumption of the poly(arylene ether) by measuring the intensity of an infrared absorbance associated with poly(arylene ether) phenolic hydroxy groups. 
     
     
         32 . The method of  claim 1 , wherein the solvent is a polymerizable aromatic solvent selected from the group consisting of styrene, vinyltoluenes, divinylbenzenes, and mixtures thereof; and wherein the method further comprises combining a polymerization inhibitor with the solution of the capped poly(arylene ether). 
     
     
         33 . The method of  claim 1 , further comprising isolating the capped poly(arylene ether) by a method selected from the group consisting of spray drying, precipitation, total isolation, devolatilizing extrusion, and combinations thereof. 
     
     
         34 . The method of  claim 1 , further comprising precipitating the capped poly(arylene ether) by a method comprising combining the capped poly(arylene ether) solution with an antisolvent to form a combined mixture, wherein the combined mixture has a weight ratio of aromatic hydrocarbon solvent to antisolvent of about 2:1 to about 5:1. 
     
     
         35 . A method of preparing a capped poly(arylene ether), comprising:
 adjusting a temperature of an aromatic hydrocarbon solvent to a temperature in the range of about 40 to about 80° C.; wherein the aromatic hydrocarbon solvent is selected from the group consisting of toluene, styrene, and mixtures thereof;   combining a poly(arylene ether) with the temperature-adjusted solvent and agitating to dissolve at least 95 weight percent of the poly(arylene ether); wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises adding the poly(arylene ether) to the solvent at a rate of about 0.4 to about 2 weight percent of the total poly(arylene ether) per minute; and wherein said combining a poly(arylene ether) is conducted in an atmosphere comprising less than or equal to 10 kilopascals partial pressure of molecular oxygen;   combining a capping catalyst with the combined poly(arylene ether) and solvent; wherein the capping catalyst comprises 4-dimethylaminopyridine;   combining a capping agent with the combined poly(arylene ether), solvent, and capping catalyst; wherein the capping agent is selected from the group consisting of acrylic anhydride, methacrylic anhydride, and mixtures thereof; and   maintaining the combined capping agent, poly(arylene ether), solvent, and capping catalyst at about 70 to about 100° C. for about 40 to about 120 minutes to form a solution of the capped poly(arylene ether).   
     
     
         36 . A method of preparing a capped poly(arylene ether), comprising:
 adjusting a temperature of an aromatic hydrocarbon solvent to about 40 to about 80° C.; wherein the aromatic hydrocarbon solvent is selected from the group consisting of toluene, styrene, and mixtures thereof;   combining a poly(arylene ether) with the temperature-adjusted solvent and agitating to dissolve at least 95% of the poly(arylene ether); wherein said combining a poly(arylene ether) is conducted in an atmosphere comprising less than 10 kilopascals partial pressure of molecular oxygen; wherein said combining a poly(arylene ether) with the temperature-adjusted solvent comprises adding the poly(arylene ether) to the solvent at a rate of about 0.4 to about 2 weight percent of the total poly(arylene ether) per minute; and wherein the solvent and the poly(arylene ether) are used in a weight ratio of about 1:1 to about 3:1;   combining a capping catalyst with the combined poly(arylene ether) and solvent; wherein the capping catalyst comprises 4-dimethylaminopyridine; wherein the capping agent and the capping catalyst are used in a molar ratio of about 4:1 to about 10:1, and wherein the poly(arylene ether) and the capping agent are used in amounts such that a molar ratio of capping agent to hydroxy groups in the poly(arylene ether) is about 2:1 to about 4:1;   combining a capping agent with the combined poly(arylene ether), solvent, and capping catalyst; wherein the capping agent comprises methacrylic anhydride; and   maintaining the combined capping agent, poly(arylene ether), solvent, and capping catalyst at about 70 to about 100° C. for about 40 to about 120 minutes to form a solution of the capped poly(arylene ether).